Azodyestuff



Patented Sept. 19, 1933 UNITED STATES- ratios Hilger, Leverlnlsen-Wiesdorf,

Germany, as-

signors to General Aniline Works, Inc., New

York, N. Y., a corporation of No Drawing. Application October 12,

Delaware Serial No. 637,550, and in Germany October 4 Claims. (01. 260-75) The present invention relates to new azo-dyestuffs, more particularly it relates to dyestuffs which may be represented by the probable general formula:

wherein A stands for the radical of a tetrazotized p.p'-diaminodiphenyl, B stands for the radical of an ortho-hydroxy-carboxylic acid of 0 the benzene series, C stands for the radical of a diazotized l-amino-2-naphtholether or a sulfonic acid thereof and D stands for a radical of a l-amino-8-naphthol-sulfonic acid or an N-substitution product thereof. I As compounds standing for A there may be mentioned by way of example, benzidine, tolidine, dichlorobenzene, dianisidine, benzidinemonoand -disulfonic acids, benzidinernonoand -dicarboxylioacids and benzidinesulfone of the formula:

soz B stands, for example, for salicylic acid andv cresotinic acid, C stands, for example, for the methyl, ethyl, propyl, benzyl, hydroxyethyl or glycol ether of l-arnino-Z-naphthol or its 6- or 7-f sulfonic acids or the acidsuli uric acid ester of the hydroxyethylor glycol ether, D stands for example for 1-amino-8-naphtholi-sulfonic acid, -2.i-disulfonic acid, -3.6-disulfonic acid, LS-di sulfonic acid or an N-substitution productthereof, such as an N-alky, -aralkyl, -aryl or -acyl-substitution product, for example for a 1-ethylamino-, 1-benzyla1nino-, 1-phenylamino-, l-acetylaminoor l-benzoylamino-8-naphthollllOllO- or -disulfonio acid. I

Our new dyestuffs are obtainable in a convenient manner by tetrazotizing a p.p-diaminodi phenyl, coupling on the one side with an orthohydroxy-carboxylic acid of the benzene series, further-coupling the'intermediate product with a 1-amin02-naphtholether or a 6- 01" -7-sulfonic acid thereof, diazotizingthe aminodisazodyestuif obtained and finally coupling with one molecular proportion of a 1--amino-8-naphtholsulfonic acid or an N-substitution product thereof.

Our new dyestufis are in form of their alkali metal salts generally dark powders, soluble in water, dyeing cotton generally clear green shades of good fastness properties.

The invention is illustrated by the following examples, without being limited thereto:

Example 1.-18,6 parts by weight of benzidinehydrochloride are diazotized in the usual manner with 10 parts by weight of sodium nitrite and hydrochloric acid. The tetrazo solution thus obtained is rendered alkaline and coupling is performed in alkaline solution with 11,0 parts by weight of salicylic acid; thenthe solution is rendered acid to acetic acid and coupling is performed with l-amino-2-naphtholethylether-6- sodium sulfonate. The aminodisazodye'stuif formed is isolated, washed with dilute aqueous acetic acid, dissolved in Water and diazotized in the usual manner with excess sodium nitrite and hydrochloric acid; the diazo compound formed is filtered and coupled in dilute pyridine solution with 1 acetylamino 8 naphthol 3.6 disulfonic acid. The dyestuii having in the free state the following formula:

SOaH

dyescotton from a Glaubers green shades.

By substituting the l-acetylarnino-8-naphthol- 3.6-disulfonio acid by l-benzoylamino-i-naphsalt bath powerful thol-3.6-disulionic acid a dyestu'fi having similar group is coupled with 1-amino-2-naphtho1-glycol ether-inonm'sulfuric acid ester. The aminodisazodyestuil formed is isolated in the usual manner, dissolved in aqueous ammonia, then sodium nitrite, is added and the solution is rendered acid to Congo by the addition of hydro- 2 chloric acid. diazo compound is isolated and the final coupling is performed with l-acetylamino- 8-naphthol-3.G-disulfonic acid in dilute aqueous pyridine solution.

The dyestuff having in thefree state the-following formula:

tained when substituting the dichlorobenzidine by benzidine-3-sulfonic acid, 3.3-disulfonic acid and 3.3-dicarboxy1ic acid, or by substituting the esterified naphtholether by 1-amino-2-benzyloxyor l-amino-2-phenoxy-naphthalene-6- or T-sulfonic acid.

HOaS--OCH2 CiHs (1112 ('10 00011 1B3 2133 0 Ho 1\TH HO ON:N C N=N N=N-@ son noas 3 dyes cotton from a Glaubers salt bath green We claim: shades. 1. The azodyestuiis of the probable general Dyestuffs having similar properties are obformula:

tained when substituting the salicylic acid by o-cresotinic acid of the formula:

OIOOH or by substituting the l-acetylamino-S-naphthol- 3.6-disulfonic acid by l-acetylamino-8-naphthol- 4.6-disu1fonicor -monosulfonio acid or by 1- benzoy1amin0-, l-ethylaminoor 1-phenylamino- 8-naphthol3.6-, or 4.6-disulfonic acid or 4- monosulfonic acid.

COOH

I I y y The aminodisazodyestuff formed is isolated, dissolved in dilute aqueous ammonia, sodium nitrite is added thereto, and the solution is rendered acid,

. (300E C1 Cl dyes cotton from a Glaubers salt bath olive green shades.

Dyestuffs having similar properties are obwherein A stands for the radical of a tetrazotized p.pdiaminodiphenyl, B stands for the radical of an ortho-hydroxy-carboxylic acid of 1 2. The azodyestufls of the probable general formula:

i (y-z H0 N-p' N=N 3 Z Z alkali metal salts generally dark powders, soluble in water and dyeing cotton generally clear green shades of good fastness properties.

the sulfonic acid group or the iis 3. The azodyestuffs of formula:

OOOH

110 R N=N wherein y and y' stand for hydrogen, alkyl, alkoxy, halogen, the sulfonic acid group or the carboxylic acid group, one 2 stands for hydro- COOH gen and the other 2 stands for hydrogen or the sulfonic acid group, n stands for the number one or'two, and wherein the benzene nucleus R may be substituted by alkyl, being the probable general in form of their alkali metal salts generally dark powders, soluble in water and dyeing cote CHa (SOaH) 2 0.0211 HO N ton generally clear green shades of good fastness properties.

4. The azodyestuff of the following formula:

dyeing cotton from a Glaubers salt bath powerful green shades.

CARL TAUBE. JOSEF HILGER. 

